Process for breaking petroleum emulsions



Patented Apr. 10, 1945 PROCESS FOR'BREAKING PETROLEUM EMULSIO S MelvinlDe Groote, University City, and Bernhard Keiser, Webster Groves, Mo.,'assignors to Petrolite Qorporatiom'Ltd Wilmington, Del., a corporationof Delaware No Drawing. Application March 9, 19413,

' Serial N 0. 478,594

Claims. ((1252-3411) This invention relates primarily to the resolutlonof petroleum emulsions.

One object of our invention is to provide a novel process for resolvingpetroleum emulsions oi the water-in-oil type, that are commonly referredtoes cut oil, roily oil," emulsified oil,

etc., and which comprisennedrpplets of naturally-occurring watersor-brines dispeTsed in a more or less permanent state throughout the oilwhich constitutes the continuous phase of the emulsion.

Another object of our invention is to provide an economical and rapidprocess for separating emulsions which have been prepared undercontrolled conditions from mineral oil, such as crude petroleum andrelatively soft waters or weak brines. Controlled emulsification andsubsequent demulsification under conditions just mentioned,

is of significant value in removing impurities, particularly inorganicsalts, from pipeline oil.

a The demulsifler or demulsifying agent employed in our process consistsof acylated derivatives obtained by reaction between a low molal dialkylcarbonate, particularly diethyl carbonate, and alkanolamines, includingthe ether type, i. e., such alkanolamlnes in which a carbon atom chainis interrupted at least once by an oxygen atom. Such alkanolamines mayhave an alicyclic radical, such as a cyclohexyl radical, an aralkylradical, or an aryl radical attached to an amino nitrogen atom. In otherwords, one is not limited to the use of materials such asmonoethanolamine, diethanolamine, triethanolamine, monopropanolamine,dipropanolamine, tripropanolamine, monobutanolamine, dibutanolamine,tributanolamine, or ether type derivatives obtained by treating thepreceding with ethylene oxide, propylene oxide, glycid, or the like.

If desired, one may treat an alkylamine, such as vamylamine, octylamine,decylamine, or the like,

with one or more moles of ethylene oxide, propylene oxide, or the like,so as to obtain a suitable reactant. The same is true in regard toalicyclic amines, such cyclohexylamine, or in regard to aralkylamines.It is also true in regard to various arylamines', such as aniline, andthe like. It is to be noted that the alkanolamine need not be a tertiaryamine, but may be a primary or a secondary amine. Thus, the expression"alkanolamine is employed in the present instance to indicate that theremust be present at least one nitrogenlinked alkanol group, including thetype, as previously stated, in which the carbon atom chain isinterrupted at least once by an oxygen atom.

One may, of course, use polyamino compounds, such as, for example, theproducts obtained by treating ethylene diamine with ethylene oxide so asto introduce at least 4 hydroxyethyl radicals. The acyl radical maybeintroduced at any convenient stage, for instance, before the aminocontaining reactant has been combined with the low molal dialkylcarbonate, or afterwards. Other low molal carbonates which may beemployed include dimethyl ester, methyl ethyl ester, methyl propylester, dipropyl ester, dibutyl ester, etc.

The acyl group which is introduced is derived from detergent-forming'monocarboxy acids containing eight carbon atoms or more, and not morethan 32 carbon atoms, and are characterized by the fact that theycombine with alkalis to produce soap or soap-like materials. Thesedetergent-forming acids include fatty acids, resin acids, petroleumacids, etc. For the sake of convenience, these acids will be indicatedby the formula R.CO0H. Certain derivatives of detergent-forming acidsreact with alkali to produce soap or soap-like materials, and are theobvious equivalent of the unchanged or unmodified detergent-formingacids; for instanceinstead of fatty acids, one might employ thechlorinated fatty acids. Instead of the resin acids, one might employthe hydrogenated resin acids. Instead of naphthenic acids, one mightemploy brominated naphthenic acids, etc. "Acids obtained by theoxidation of petroleum fractions or waxes may be employed. This type ofacid may also be subjected to various modifications, provided suchmodifications still retain detergent-forming properties.

In some instances, more than one type of reaction may take place. Forexample, there may be aformation ota urethane and an amino estersimultaneously.

In view of what is said hereinafter, it is. ap-

' parent that the compounds contemplated herein may be considered asacylation derivatives of esters of carbamicand carbonic acids, and moreparticularly, Jesters containing at least one hi trogen-linked alkanolradical, and in which the acyl radical isthat of a. detergent-formingmonocarboxy acid having at least 8 and not more than 32 carbon atoms;

For the sake of clarity, the following reaction types are presented asillustrating the class .of

compounds formed. In all instances, theyrepresent intermediate productsand are acylated sub- OHCllHt I SEC: 4

- canon 221, dated June 8, 1937, to De Groote. Since the productstherein contemplated are acylated derivatives of substituted ureas, itis obvious that such type of material is not contemplated in the presentinstance, although we have discovered that such material of a typecontemplated in said aforementioned De Groote patent can be reacted withdiethyl phthalate, or the like, to produce more complicated types ofmaterials or chemical compounds which may be used as demulsiflers forczHtOH In reactions involving allra nol primary or water-in-oilemulsions. The Iollowing illustrate secondary amines, a more complicatedseries of reactions may take place. Indeed, in the ordinary course theresult of reaction isa xture of various products. It is. particularlytrue when the final acylated product is used as an intermediate forsubsequent reaction with a material such as diethyl phthalate, that itis immaterial for many purposes, whether a single resultant is obtainedor a mixture of resultants. Such phthalated derivatives are notcontemplated per se in this present application, either as newcompositions oi matter, new chemical compounds, or as demulsifiers forwater-in-oli emulsions.

The ioregolng is illustrated by considering a very simple aspect, forInstance, a reaction iri= vclving cliethanolamine and diethyl carbonate.At least three possible reactions uggest them= selves immediately:

The same're'action as alcove illustrated will take place in connectionwith other materials, such as dipropanolamine, dibutanolamine, and alsoin connection with secondary amines or the type ethyl ethanolamine,ethyl propanolamine, ethyl butanolamine, propyl ethanolamine, propylpropanolamine, cyclohexyl ethanolamine, benzyl ethanolamine, phenylethanolamine, etc. This is also tru in regard to primary amines, such asmonoethanolamine, monopropanolamine, monobutanolamine,m0nopentano1amine, monohexanclamine, etc,

Reconsidering the three reactions immediately preceding, it is obviousthat they may be considered as substituted ureas, substituted urethanes,and carbonic acid esters. The urethanes are, of course, esters ofcarbamic acid. It is also obvious that the products of reaction abovedescribed, the esters. urethanes, the substituted ureas, etc., can betreated with ethylene oxide, or some other reagent having a reactiveethylene oxide ring, and subsequently, acylated with a high molalmonocarboxy acid. In this connection, reference is made to U. 8. PatentNo. 2,083,-

added examples:

(till 0 6' M NCzHtO H+CZH50. OCzHH-H OC2H4 CH0: 4 ZHtOH CQHAO H C:H5.0.0.0.CsH5

BHCOR camels CQHt-O-I-IO-CQHE; HO one, soon coca GEE/30H HOCrEtIntermediate product, Example Z Two pound moles of triethanolarnhie wereheated for approrimately fi-l2 hours under a reflux condenser with onepound mole of diethyl carbonate. The refluxing temperature wasapproximately C. At the end or" the reaction period the mixture wassubjected to distillation so asto remove the ethyl alcohol formed andany unreacted diethyl carbonate.

Intermediate product, Example 2 The same procedure was followed as inIntermediate product, Example 1, preceding, except that one pound moleof triethanolann'ne was employed for three pound moles of diethyl' carbonate.

Intermediate product, Example 3 The product obtained in Intermediateproduct, Example 2, preceding, was heated further until the resultantmass represented a viscous material almost approaching a rubber-likecon- Intermediate product, Example 4 Triethanolauune, which had beentreated with ethylenooxide in the ratio of three moles of ethylene oxidefor one mole of triethanolamine, was substituted as the tertiary aminein the preceding examples.

Intermediate product, Example Triisopropanolamine was substituted {ortriethanolamine in the preceding examples.

Intermediate product, Example 6 V Two pound moles of diethanolamine werereacted with one pound mole of diethyl carbonate in the same manner asdescribed in Intermediate product, Example 1, preceding. Analysisindicated that the final product contained approxi mately 50% of aurethane or substituted urea and 50% of an amino ester. I

Intermediate product, Example 7 Two pound moles of hydroxyethyl ethylenediamine were reacted with one pound mole of diethyl carbonate in themanner described under Intermediate product, Example 1, preceding.

Intermediate product, Ezrample 8 The sanie procedure was followed as inthe preceding example, except that tetraethanol tetraethylene pentaminewas substituted in place of hydroxyethyl ethylene diamine.

Intermediate product, Example 9 One pound mole ofj hydroxyethyl ethylene(11- amine was treated with three to five pound moles of ethylene oxide,so as to convert all amino hydrogen atoms to hydroinrethyl radicals. The

product so obtained-was substituted for hydroxy-l ethyl ethylene diaminein Example '7, precediria.

Intermediate product, Example 10 Tris(hydroxymethyl) aminomethane wassub stitutedfor triethanolamine in Intermediate]- product, Example 1,preceding. 'When this r eactant was used, the yield was considerablyless than with previous examples, especially those.

in which triethanolami-ne was reported. Ap-

proximately /2% of .sodiumbicarbonate was have been described andillustrated by the-exclude such as an ester or amide. This means thatfor practical purposes it is most convenient to use the higher fattyacids as a source of the high molal monocarboxy detergent-formingradical, for the reason that such acids are available in the form of anester, i. e., the glyceride. In other instances, and especially when thereaction takes place at a decidedly lower temperature, one may employ alow molal monohydric alcohol ester of the detergent-forming acid, suchas a methyl ester, an ethyl ester, or a propyl ester of the fatty acidor detergent-forming acid. In other words, ethyl ri=cinoleate, ethyloleate, ethyl naphthenate, ethyl abietate, etc., are particularlydesirable reactants. The methyl esters and propyl esters are alsodesirable. The corresponding amides derived by reaction between one moleof the acids and ammonia'may also be used with the subsequent liberationof ammonia during the reaction. What has been said in this connection isreadily illustrated by subsequent examples.

Another procedure to obviate such difficulties of decomposition hasalready been suggested by the formulas or reactions previouslypresented. One solution resides in introducing the acyl radical of thehigh molal detergent-forming acid into the desired amino moleculeor compound prior to reaction with diethyl carbonate, or its equivalent. Forinstance, it is well known that any of the monocarboxy detergent-formingacids of the kind herein contemplated as such, or in any equivalentform, includingthe acyl chloride, amide or acid can be reacted with avariety of primary or secondary amines containing an alkanol radical,such as monoethanolamine, diethanolamine,- monopropanolamine,dipropanolamine, aminometh'ane, or the like, to produce amides in whichthere is present at least one amino radical.

Other suitable reactants ofthis type inethylethanolamine,cyclohexylethanolamine, phenylethanolamine, benzylethanolamine,

' and the like. The manufacture of such amides amples of Intermediateproducts immediately V preceding. Indeed, it is not always possible topredict the stability of diethyl carbonate towards .aqueous acids, evenat normal room temperature. 7

The best test in any instance is an actual laboratory experiment todetermine whether or not decompositionand liberation of carbon dioxidetakes place. For these reasons, subsequent acylation of intermediateproducts of the kind previously described is best conducted by anonacidic fatty acid derivative, rather than the fatty acid derivativeitself. In other words, if one'attempts to acylate materials of the kindpreviously described by means of oleic acid,

ricinoleic acid, abietic acid, naphthenic acid, or the like, one findsthat decomposition takes place, under conditions required to give thedesired resultant. One suitable procedure is to resort to a functionalequivalent of the acid,

numeral 0, 1 or 2, with the proviso that is well known and requires nofurther elaboration, although some subsequent examples may illustratethe formation of such amides by the oxyalkylation of an amide.

In regard to the acylated aminoalcohols used as reactants, one typ amonoamino type, is described in U. S. Patent No. 2,225,24, datedDecember 24, 1940, to De Groote and Wirtel. Said patent describes indetail the manufacture of compounds 01 the following iormula:

. account N(T) .w'

(OHIhHa-{u in which R.C0O represents theoxyaeyl radical derived from amonobasio detergent-forming acid; T represents a hydrogen atom or anonhydroxy hydrocarbon radical or the acylated radical obtained byreplacing a hydrogen atom of I the hydroxyl group of an alkylol radicalby the acyl radical of a monobasic carboxy acid having less than 8carbon atoms; n represents a small whole number which is less than 10; mrepresents the numeral 1, 2 or 3; m represents the numeralO, 1 or 2; andm represents the m+m'+m" equals 3.

A similar type of compound, which contains an ether linkage, isdescribed in US. Patent tris(hydroxymethyl) No. 2,259,704, dated October21, 1941, to Monson and Anderson. In said patent there is a descriptionof acylated aminoethers containing:

(a) A radical derived from a basic hydroxyaminoether, and said radicalbeing of the kind containing at least one amino nitrogen free fromattached aryl and amido-linked acyl radicals; said hydroxyaminoetherradical being further characterized by the presence of at least oneradical derived from a basic hydroxyamine and being attached by at leastone ether linkage to at least one radical selected from the classconsisting of glycerol radicals, polyglycerol radicals, polyglycolradicals, basic hydroxyamine radicals, amido hydroxyamine radicals, andaryl alkanolamine radicals; said basic hydroxyaminoether radical beingcharacterized by containing not over 60 carbon atoms; and '(b) An acylradical derived from a detergentforming monocarboxy acid having at least8 carbon atoms and not more than 32 carbon atoms; said acylatedaminoether being additionally characterized by the fact that saidaforementioned acyl radical is a substituent for a hydrogen atom of analcoholic hydroxy radical.

Although primarily, raw materials, such as triethanolamine,ethyldiethanolamine, and the like, are most frequently employed in themanufacture of the acylated aminoalcohol, it is understood that suchmaterials may be reacted with an oxyethylating agent, such as ethyleneoxide, propylene oxide, or the like, to produce comparable materialswhich also are well known compounds. .(See also U. S. Patents Nos.2,228,986, '7, 8, and 9, all dated January 4, 1941, to.De Groote,Keiser, and Blair.) If desired, the acylated aminoalcohols of the kindpreviously forming acid acyl radical and at least one hydescribed may besubjected to a subsequent oxyalkylation step, i. e., treatment withethylene oxide or the like. For example, the ester derived fromricinoleic acid and triethanolamine could be subjected to treatment withethylene oxide, propylene oxide, or the like. As has been previouslypointed out, such acylated aminoalcohols containing at least one basicamino nitrogen atom, need not be obtained from monoamines, ormonoaminoalcohols, but may, in fact, be obtained from polyaminoalcohols.Thus, hydroxyethyl ethylenediamine may be treated with three moles ofethylene oxide, so 'as to obtain tetra- (hydroxyethyl) ethylenediamine.Such product can be readily acylated with a high molaldetergent-forminglacid, Similarly, diethylenetriamine can be treatedwith four moles of ethylene oxide, so as to yield a tetra-substitutedproduct. The compound obtained can be acylated with two moles of asuitably selected detergent-forming acid, for example, a higher fattyacid, to give a suitable acylated aminoalcohol having at least two basicnitrogen atoms. Furthermore, in the broadest aspect, one is not limitedto acylated derivatives in which the acyloxy radical of thedetergent-forming acid enters into the aminoalcohol, but one may employcompounds in which the acyl group, as distinguished from the acyloxygroup, is introduced into the amino reactant. For example,ethylenediamine, or diethylenetriamine, may be treated with adetergent-forming monocarboxy acid, so as to yield the acylatedpolyamine. Such polyamine can then be treated with ethylene oxide or thelike, so as to convert it into an aminoalcohol. Insofar that there are,two or more amino nitrogen atoms present, obviously. there must be atleast one basic nitrogen ,from the acyloxy radical,

ammonia, may be obtained from primary amines.

such as amines in which a hydrogen atom linked to a nitrogen atom hasbeen replaced by an alkyl radical, an aralkyl radical, an alicyclicradical, an alkylol radical, or the type of radical in which the carbonchain has been interrupted at least once by an oxygen atom. Examples ofsuch amines are amylamine, cyclohexylamine,

lbenzylamine, monoethanolamine, tris(hydroxymethiyDaminomethane, etc.Polyamino types may also be employed, such as ethylenediamine,bis(hydroxyethyl) ethylenediamine, etc. If one starts with ammonia, oran amine free from a hydroxylated radical, it is obvious that the amidesso obtained, for instance, oleoamide, ricinoleoamide, amyloleoamide,amylricinoleoamide, or the like, can be treated with one or more molesof an oxyethylating agent, such as ethyleneoxide, propyleneoxide,butyleneoxide, glycid, or the like, to give a high molal substitutedamide having at least one monocarboxy detergentdroxylated hydrocarbongroup, or the equivalent,

.wherein the carbon atom chain is interrupted at least once by oxygen.The amine need not be basic, and thus aniline, phenylethanolamlne, orthe like, may also be employed as a primary reactant. Obviously,however, amides can be obtained as conveniently from a fatty acid, forexample, and monoethanolamine, as would be possible by first reactingthe fatty acid or its equivalent, such as the ester, with ammonia, andthen subjecting the unsubstituted amide to oxyethylation. The productionof such amides, and, as a matter of fact, polyamides derived fromsuitable polyamines, is well known and requires no further elaboration.The presence of a basic nitrogen atom, i. e., a nitrogen atom notdirectly linked to either an aryl group, or an acyl radical, is riotobjectionable, and may be desirable. For instance, one might reacthydroxyethyl ethylene diamine with ricinoleic acid, so as to introducethe acyl radical, as distinguished It is to be noted that some of thehigh molal substituted amides are polyfunctional, in that two or morehydroxy hydrocarbon radicals, or their equivalents, are introduced.Furthermore, there is no objection to using the oxyethylating agent insubstantial multiple proportions, i. e., there is no objection tointroducing an ether linkage'which recurs a number of times. Althoughreactants of the kind described immediately preceding are well knovm, afew examples will be given:

Basic acylated aminoalcohols, Example 1 of the following formula:

OHRC 00 01K:

OHCzHr- Basic acylated aminoalcohols, Example 2 v The same procedure isfollowed as in the preceding example, except that the triethanolamine istreated with three moles of ethylene oxide prior to acylationwith-ricinoleic acid.

.Basic acylated aminoalcohols, Example 3 Ethyldiethanolamine issubstituted for triethinolamine in Examples 1 and 2, preceding.

Basic acylated aminoalcohols, Example 4 Trlisopropanolamine orpropyldiisopropanolanine is employed, following the same procedure isdescribed in Examples 1 to 3, preceding.

Basic acylaiied aminoalcohols, Example 5 Hydroxyethyl ethylenediamine isreacted with Returning now to consideration of acylated K ;hree moles ofethylene oxide and then with one nole of ricinoleic acid, so as to givea compound )1 the following compositionz' ormcoocim canon NCzHaN 4OHCiH4 CrHaOH Basic acplated aminoalcohols, Example 6 Diethylenetriamineis treated with-four moles 1 ethylene oxide and then with two moles oficinoleic acid.

The compounds described in the preceding eximples are well knowncompositions and the method of preparation is well known.

Hydroxylated substituted high molal amides,

Example 1 Hpdroxylated substituted high molal amides, Example 3 Onepound mole of ricinoleic acid is reacted with one pound mole of2-amino-2-methyl-1,3- ropanediol to give the corresponding amide.

Hydroxylated substituted high molal amides,

' Example 4 products by reaction involving reactants exemplified'byIntermediate Examples 1 to 10, inclusive, one need only consider a fewspecific examples, such as the following, which illustrate procedure sothat more elaborate description is unnecessary:

- Acylated product, Example 1 Three pound moles of a material or thekind described under Intermediate product, Example 1, preceding, washeated for approximately 2 hours at 200 C. with one pound mole or triricinolein.

'Acylated product, Example 2 The same procedure'was followed as in.Acylated product, Example 1, preceding, but instead oi usingIntermediate product, Example 1, preceding, there was substitutedvarious other intermediate products, as described under the heading"Intermediate product, Example 2 to Intermediate product, Example 10,inclusive.

Acylated product, Example 3 In view or the composition of some of theproducts described under Intermediate products, Ex-

amples 2-10, preceding, it is obvious that more than one acyl radicalcould be introduced. For

instance, three pound moles of an intermediate 3 product or the kindexemplified by Intermediate product, Example 1, was reacted with twopound moles of triricinolein, so as to yield a polyacylated product. I

Acylated product, Example 4 Two pound moles of ethanol ricinoleoamideobtained by reaction between ricinoleic acid and ethanolamine, wereheated with one poundmole of diethyl-carbonate. (See Hydroxylaiedsubstituted high molal amide, Example 1.") The-reaction was -conductedin the presence of %%,;so

dium carbonate as a catalyst. The material was refluxed at approximately120 C. for eight hours and then the distillate removed in the customarymanner. I.

One pound mole of ricinoleic acid is reacted "1th one pound mole of2-amino-2-ethyl-1,3-proanediol to give the corresponding amide.

Hydroxylated substituted high molal amide Example 5 I One pound mole ofricinoleic acidis reacted 'ith one pound mole oitris(hydroxymethyl)amiomethane to give the corresponding amide.

Hydroxylated substituted high molal amides, 7

Example 6 One pound mole of ricinoleic acid is reacted with 1e poundmole of hydroxyethyl ethylenediamine I give the corresponding amide. I

Hydroxylated substituted high molal amide Example 7 One pound mole ofdiethylenetriamine is re- :ted with one pound mole of ricinpleic aeid tove the corresponding amide, which is then re- :ted withonepound mole ofethylene oxide give the corresponding hydroxyethylamide.

Acylated pro uct, Example 5 Diethyl ricinoleoamide derived by reactionbetween ricinoleic 'acid and diethanolamine was substituted for ethanolricinoleoamide in the preceding example. (See Hydroxylated substitutedhigh molal amide, Example 2.) Approximately one-half percent of sodiumbicarbonate was added as a catalyst during the reaction.

Acylated product, Example 6 The amide derived by reaction between ricinoleic. acid and tris (hvdroxymethyl)aminometlrone was substituted fordiethanol ricinoleoamide in the preceding example.

00 substituted high molal amide, Example 5.) Appositions of matter ordemulsifying agents by.

proximately one-half percent of sodium bicarbonate was added as acatalyst during the reaction; As tothe preparation of the desired newcomreactions involving diethyl carbonate, or its equivalent, and anacylated amino alcohol, reference is made to the following examples:

Acz lated product, Example 7 Two pound moles of a type of materialexemplified by Basicacylated amino alcohols, Ex-

ample 1, is reacted with one pound mole of diethyl carbonate. Thereaction is conducted in 73 the presence of one-half of 1% of sodium bi-(See Hydroxylated referred to as higher fatty acid compounds.

carbonate as a catalyst. The material is refluxed at approximately 120C. for 8 hours and the distillate then removed in the customary manner.

Acylated product, Example 8 Two pound moles of materials exemplified byBasic acylated amino alcohols, Example 2 are reacted with one pound moleof diethyl carbonate in the same manner as preceding Example 7.

Acylated product, Example 9 the acyl group indicated by the radical RCO.It.

is our preference, however, to use fatty acid compounds as the source ofsuch high molal acyl radical. Such acid compounds are commonly We preferto use fatty acid compounds derived from acids having 18 carbon atoms,and more-especially, unsaturated fatty acid compounds. We particularlyprefer to use compounds obtained from oleic acid, ricinoleic acid,linoleic acid, linolenic acid, etc. We have found that the mixture offatty acids obtained from soyabean oil, peanut oil, teaseeel oil,linseed oil,,. corn oil,'cottonseed oil, and the like, would beparticularly desirable, after conversion into suitable compounds.

Attention is again directed to the fact that nificant, because saidreagents undoubtedly have solubility within the concentration employed.This same fact is true in regard to the material or materials employedas the demulsifying agent of our process.

We desire to point out that the superiority of the reagent ordemulsifying agent contemplated in our process is based upon its abilityto treat certain emulsions more advantageously and at a somewhat lowercost than is possible with other available demulsifiers, or conventionalmixtures thereof. It is believed that the particular demulsifying agentor treating agent herein described will find comparatively limitedapplication, so far as the majority of oil field emulsions areconcerned, but we have found that such a instead of using reactants ofthe kind described,

such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil,etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol,ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexylalcohol, octy alcohol, etc., may be employed as diluents. Miscellaneoussolvents, such as pine oil, carbon tetrachloride, sulfur dioxide extractobtained in the refining of petroleum,-etc. may be employed asdiluents.- Similarly, the material or materials employed' as thedemulsifying agent of our process may be addemulsifying agent hascommercial value, as it will economically break or resolve oil fieldemulsions in a. number of cases which cannot be treated as easily or atso low a cost with the demulsifying agents heretofore available.

In practising our process for resolving petroleum emulsions of thewater-in-oil type, a treating agent or demulsifying agent of the kindabove described is brought into contact with or caused to act upon theemulsion to be treated, in any of the various ways, or by any oi. thevarious apparatus now generally used to resolve or break petroleumemulsions with a chemical reagent, the above procedure being used eitheralone, or in combination with other demulsifying procedure, such as theelectrical dehydration process.

The demulsifier herein contemplated may be employed in connection withwhat'is commonly known as down-the-hole procedure, i. e., bringing thedemulsifier in contact with the fluids of the well at the bottom of thewell,- or at some point prior to the emergence of said well fluids. Thisparticular type of application is decidedly feasible when thedemulsifier is used in connection with acidification of calcareousoil-bearing strata, especially if suspended in or dissolved in the acidemployed for acidification.

Attention is directed to the fact that the compounds herein described,i. e., the finished products, may be considered as intermediates forsub-' sequent and further reaction. For instance, they mixed with one ormore of the solvents customarily used in connection with conventionaldemulsifying agents. Moreover, said material or materials may be usedalone, or in admixture withother suitable well known classes ofdemulsifying agents. I

It is well known that conventional demulsifying agents may be used in awater-soluble form,-

may be combined with dibasic or polybasic acid esters, such as thedialkyl esters of phthalic acid, maleic acid, citraconic acid, and thelike, to produce resinous and sub-resinous materials. They may becombined with chloracetic acid esters, such as ethyl chloroacetate, soas to give derivatives which canbe' united with tertiary amines to formquaternary compounds. They may be subjected to further oxyethylation, soas to produce additional types of wetting agents. All such variousderivatives are effective demulsifiers for crude oil emulsions of thewater-in-oil type. Furthermore, the introduction of a low molal acylradical, for instance, the introduction of an acetic acid radical,lactic acid radical, or a hydroxyacetic acid radical, is notobjectionable, and in -many instances, gives a particularly desirableHaving thus described 'our invention, what we claim as new and desire tosecure by Letters Patent is:

l. A process for breaking petroleum emulsions of the water-in-oil type,which consists in subhaving at least 8 and not more than 32 carbon atomsand is the substituent for at least one alcoholic hydroxyl hydrogen atomof an alcohol; which alcohol is in turn a hydroxylated amino ester ofthe formula:

in which R: is a member of the class consisting of alkylene andoxyalkylene radicals having not more than 4 carbon atoms in the alkylenegroup;

R2 is a member of the class consisting ofhydrogen atoms, R1(OH)nradicals, and monovalent hydrocarbon radicals having not over '7 carbonatoms; R3 is a member of the class consisting of:

radicals; and in all instances n being a small whole number.

2. The process of claim 1, wherein Rco is the acyl radical of anunsaturated higher fatty acid, and R2 is an Ri(0H)n radical, and R3 isan radicaL all occurrences of R1 being ethylene radicals, and n beingone.

,3. The process of claim 1, wherein RC0 is a ricinoleyl radical, and R2is an R1(OH)n radical, andRaisan O-R1N/ R1(0H)l radical, all occurencesof R1 being ethylene radicals, and n being one.

4. The process of claim 1, wherein RC0 is an oleyl radical, and R2 is anR1(OH)n radical, and R: is an O-Rn-N 011); radical, all occurrences ofR1 being ethylene radicals, and n being one.

5. The process of claim 1, wherein RC0 is a linoieyl radical, and R2 isan R1(OH)n radical, and R3 is an /Ra l-N ax n).

radical, all occurrences of R1 being ethylene radicals, and n being one.

IMELVIN DE GROOTE. I BERNHARD KEISER.

